JPH03128906A - Polymer for high-gloss coating - Google Patents

Abstract

PURPOSE: To obtain a coating composition capable of giving a high gloss coating by using an organic solvent solution of a reaction product obtained by reacting a saturated monocarboxylic acid with an ethylenically unsaturated epoxy functional monomer, etc.

CONSTITUTION: A polymer product in an amount of 20-100 wt.% formed by the reaction of (A) 1.0-70 wt.% saturated monocarboxylic acid (e.g. isostearic acid), (B) 1.0-50 wt.% polymerizable ethylenically unsaturated epoxy functional monomer (e.g. glycidyl methacrylate) and, if necessary, (C) 0-40 wt.% copolymerizable hydroxyl functional vinyl monomer (e.g. hydroxypropyl acrylate) and, if necessary, (D) 0-60 wt.% copolymerizable ethylenically unsaturated monomer different from component (B) and component (C) (e.g. styrene) [component (A) and component (B) having been reacted, and component (B) and component (C) and component (D) having been addition-polymerized] and 80-0 wt.% inert solvent such as xylene are incorporated to form a coating resin composition.

COPYRIGHT: (C)1991,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a hydroxyl-functional polymer prepared from components containing a saturated monocarboxylic acid and an unsaturated epoxy-functional monomer and having β-hydroxyl functionality. More particularly, the present invention relates to resinous compositions containing such polymers formed from components further containing hydroxy-functional vinyl monomers.

(Prior Art) Co-reactive reagents (e.g. polyisocyanate curing agents)
Coating compositions based on hydroxyl-functional acrylic polymers cured with are well known in the art. Although such compositions do not necessarily require the application of heat to promote curing, the compositions may be modified to accommodate the reactive groups of the curing agent (
For example, incyanato groups derived from polyisocyanates)
In a broad sense, it is considered to be a thermosetting type in the sense that it forms a cross-linked structure through the reaction between the compound and the human 1-roxyl group.

Such art-known coating compositions, when utilized (e.g., in automotive coating applications), provide good film properties at fairly high total solids contents; The excellent properties obtained with older lacquer-type coating compositions are often not achieved. Old lacquer-type coating compositions are now used less favorably than they used to, due to their low solids content (i.e., conversely, due to their high organic solvent content) when applying coatings to substrates. do not have. Furthermore, such compositions known in the art often tend not to be compatible with various pigments to the desired degree. These pigments tend to adversely affect the appearance properties of cured films prepared from compositions such as those described above, such as gloss and image sharpness (Do+>).

When pigmented and cured, it can be a durable, high-quality automotive finish with excellent gloss and DO+, and requires a high degree of buffing to obtain these excellent texture properties. It is desirable to provide a hydroxyl-functional, heat-curable (crosslinked) polymer, such as (without the need for).

The present invention is directed to achieving these objects and other objects which will become apparent to the reader below.

U.S. Pat. No. 4,818,796 to Das et al.
(A) in the presence of a no-radical initiator;

β-ethylenically unsaturated carboxylic acid group-containing monomer,
(B) refers to a hydroxyl-containing polymer containing at least 5 carbon atoms and prepared by heating (A) and a non-polymerizable epoxy compound. It has been disclosed that such hydroxyl-containing polymers can be hardened with reagents reactive with active hydrogen-containing substances (aminoblasts and polyisocyanates).
). In accordance with this patent, the method for preparing polymers of this disclosure takes into account cases in which polymerization and esterification occur simultaneously and cases in which polymerization = 13- occurs prior to esterification. Although the preparation of these polymers yields useful products, the wide range of epoxy compounds required for the preparation of the products of this patent are not readily available. The preparation of the products of this patent by a procedure of first polymerizing an unsaturated acid followed by post-esterification with a non-polymerizable saturated epoxy compound because of the selected In addition, the high temperature process for preparing the products of this patent, which contain both hydroxyl and carboxyl groups, leads to less desirable intramolecular ester reactions and intermolecular Both esterification reactions can occur.

The present invention provides, for example, thermosetting compositions that combine active hydrogen in the reaction products of the present invention with reactive curing agents to provide cured films with exceptional degrees of gloss and Do+. Many degrees of freedom are allowed in terms of reactants and methods of preparation to obtain products useful for forming. Furthermore, in the preparation of the products of Invention 14, intermolecular hydroxyl/carboxyl reactions are less likely to occur and therefore the present invention has less internal structure resulting from such undesired esterification reactions. It is thought that such products tend to be produced.

SUMMARY OF THE INVENTION The present invention provides resinous compositions containing the following polymeric products: a saturated monocarboxylic acid, a polymerizable ethylenically unsaturated epoxy functional monomer, It is optionally prepared by reacting a copolymerizable hydroxyl functional vinyl monomer and optionally at least one other copolymerizable ethylenically unsaturated monomer. The preparation of the polymeric products of the present invention is intended to effect the reaction of the carboxyl functionality derived from the saturated monocarboxylic acid with the epoxy functionality derived from the ethylenically unsaturated epoxy functional monomer. There is. To prevent undesirable side reactions, the utilization of ethylenically unsaturated carboxylic acids (such as 5-acrylic acid and methacrylic acid) is minimized or avoided. Therefore, the polymer products of the present invention are preferably prepared without the use of ethylenically unsaturated carboxylic acids.

The invention also provides coating compositions containing the polymeric products of the invention as binders.

The present invention further provides a method of coating a substrate, the method comprising the following steps (A) and (B): (A) a pigmented basecoat composition containing a film-forming resin; (B) applying a topcoat composition containing (a), (b) and (c) below to the basecoat; coating in one or more coats; (a) a polymeric product of the invention; (b) a curing agent reactive with the hydroxyl functionality of the polymeric product; and (
c) Optionally a catalyst to accelerate curing.

The present invention provides (A) the following (1), (2), (3) and (
Polymer product 20 formed from the reaction of components comprising 4)
weight = 16% to 100% by weight; and (B) an inert organic solvent from 80% to 0% by weight; that is, the above components include (1) a saturated monocarboxylic acid; (2)
Polymerizable ethylenically unsaturated epoxy functional monomer
(3) optionally a copolymerizable hydroxyl functional vinyl monomer; and (4) optionally said component (
2) and (3), wherein the epoxy functional group derived from the ethylenically unsaturated epoxy functional monomer is derived from the saturated monocarboxylic acid. The ethylenic unsaturation that has reacted with carboxyl functional groups and originates from the epoxy-functional monomer and from the optional components (3) and (4) is due to the presence of a polymerization initiator. Below,
Addition polymerization is occurring.

Additionally, the present invention is a method of preparing a polymeric product suitable for use in a thermosetting composition, comprising:
It includes reacting components containing the above (1), (2), (3) and (4).

According to a preferred embodiment, the method for preparing the polymeric phase 7-acid of the present invention comprises combining said saturated monocarboxylic acid and said polymerizable ethylenically unsaturated epoxy functional monomer.
first pre-esterifying to form a first reaction product;
The first reaction product is then polymerized together with the optional components (3) and (4) in the presence of the polymerization initiator.

According to a preferred embodiment, the method for preparing the polymer composition of the present invention comprises first adding said polymerizable ethylenically unsaturated epoxy functional monomer to said optional component (3) and (
4) to form an epoxy-functional polymerization product, which is then esterified with the saturated monocarboxylic acid.

According to a preferred embodiment, the method for preparing the polymer composition of the present invention provides that the ethylenically unsaturated epoxy-functional monomer comprises the saturated monocarboxylic acid and the optional component (
Polymerize in the presence of 3) and (4).

The present invention further provides a polymer product 1 formed from the reaction of components comprising (1), (2), (3) and (4) above.
8- as a binder, wherein the epoxy functional groups derived from the ethylenically unsaturated epoxy functional monomer in the polymer product are derived from the saturated monocarboxylic acid. reacted with carboxyl functional groups and derived from the ethylenically unsaturated epoxy functional monomer and the optional components (3) and (4).
) is subjected to addition polymerization in the presence of a polymerization initiator.

The present invention further provides a method for coating a substrate, comprising:
) applying a pigmented basecoat composition containing a film-forming resin to a substrate in one or more coats to form a basecoat; and (B) below (a), (b) and (c). ) on the basecoat in one or more coats, i.e., the topcoat composition comprises: (a) (1) 1.0 weight saturated monocarboxylic acid; % to 70% by weight, (2) 1.0% by weight of polymerizable ethylenically unsaturated epoxy functional monomer
~50% by weight, (3) 0% to =19-40% by weight of a copolymerizable hydroxyl-functional vinyl monomer, and (4) a copolymerizable ethylenic monomer different from components (2) and (3). A polymeric product formed from components containing from 0% to 60% by weight of unsaturated monomer, wherein epoxy functional groups derived from the ethylenically unsaturated epoxy functional monomer are present in the polymeric product. (b) a curing agent reactive with the hydroxyl functionality of the polymeric product; and (c) optionally and contains an effective amount of a curing accelerating catalyst.

(Structure of the Invention) The polymer product of the present invention is produced by the following (1), (
2), (3) and (4) are prepared by reacting components containing: (1) saturated monocarboxylic acid from 1.0% to 10% by weight, preferably 10
(2) 1.0% to 50% by weight of a polymerizable ethylenically unsaturated epoxy functional monomer;
(3) copolymerizable hydroxyl-functional vinyl monomer 20-0 to 40% by weight, preferably 10% to 40% by weight;
% by weight, and (4) from 0% by weight of a copolymerizable ethylenically unsaturated monomer different from said components (2) and (3).
60% by weight, preferably 20% to 50% by weight. The above percentages are based on the total weight of reactants. The epoxy functionality derived from the ethylenically unsaturated epoxy functional monomer reacts with the carboxyl functionality derived from the saturated monocarboxylic acid during the preparation of the polymeric products of the invention. The resinous composition of the present invention generally comprises (
A) 20% to 0% by weight of the polymer product, and (B) 80% to 0% by weight of a compatible inert organic solvent and/or diluent.

Examples of saturated monocarboxylic acids of component (1) for preparing the polymeric products of the invention include: pentanoic acid, isostearic acid, neodecanoic acid, isodecanoic acid, nonanoic acid, neoheptanoic acid, Cyclohedoxanecarboxylic acid, benzoic acid, toluic acid, and exon chemical (
ECR from EXXON Chemical (USA)
-903 is a mixture of aliphatic mono-21-carboxylic acids. The monocarboxylic acid can be aliphatic or aromatic, but aliphatic acids are preferred.

Usually, saturated monocarboxylic acids that are amorphous at room temperature are used and are preferred. Typically monocarboxylic acids having 6 to 18 carbon atoms are used, especially those with a branched structure. As used herein, the term "saturated" in the phrase "saturated monocarboxylic acid"
Intended to indicate absence of ethylenic unsaturation. However, there is no intention to exclude aromatic unsaturation found, for example, in the benzene ring, such as in benzoic acid.

Examples of polymerizable ethylenically unsaturated epoxy functional monomers of component (2) for preparing the polymeric products of the present invention include glycidyl niaacrylate, glycidyl methacrylate, allyl glycidyl ether, Metaallyl glycidyl ether, ethylenically unsaturated monoisocyanates (e.g. meta-isopropenyl-α, α-
dimethylbenzylisocyanate) and a hydroxyl-functional 22-monoepoxide (e.g. glycidol) in a 1:1 manner (
molar ratio) adducts, and glycidyl esters of polymerizable polycarboxylic acids (e.g., maleic acid, fumaric acid, and crotonic acid). Epoxy-functional acrylic esters such as glycidyl acrylate, epoxy-functional methacrylic esters such as glycidyl methacrylate, or mixtures thereof are preferred, with glycidyl methacrylate being particularly preferred.

Examples of copolymerizable hydroxyl-functional vinyl monomers of component (3) for preparing the polymeric products of the invention include: hydroxyl-functional acrylic and methacrylic esters, such as , hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, and butanediol monoacrylate); hydroxyl-functional vinyl ethers (e.g., hydroxybutyl vinyl ether); A functional vinyl monomer (for example, an adduct of 1 mole of ε-caprolactam and 1 mole of hydroxyethyl acrylate). Typically, copolymerizable hydroxyl-functional vinyl monomers are used in preparing the polymeric bioacids of the present invention. In particular, the polymeric products of the present invention are intended to be cured via reaction of hydroxyl with reactive curing agents, such as organic polyisocyanates, polyanhydrides, and aminoblasts such as melamine-formaldehyde resins. Used when it is desired to provide primary hydroxyl groups to enhance hardening of the product.

Examples of other copolymerizable ethylenically unsaturated monomers, different from components (2) and (3), corresponding to component (4) for preparing the polymeric products of the invention include: Included are alkyl nitacrylates (e.g., methyl acrylate, ethyl acrylate, butyl acrylate, propyl acrylate, 2-ethylhexyl acrylate, and imbornyl acrylate); alkyl methacrylates (e.g., 24-methyl methacrylate, methacrylate) butyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate, lauryl methacrylate, and inbornyl methacrylate); amide, N-ethoxymethylacrylamide, and N-ethoxymethylmethacrylamide); unsaturated nitriles (e.g., acrylonitrile, methacrylonitrile, and ethacrylonitrile); vinyl aromatic hydrocarbons (which optionally contain e.g. , substituted with a halogen atom: e.g.
styrene, α-methylstyrene, α-chloromethylstyrene, and vinyltoluene); and vinyl aliphatic hydrocarbons (which are optionally substituted, e.g. with halogen atoms: e.g. vinyl acetate and vinyl chloride) . Typically, at least one of these other copolymerizable ethylenically unsaturated monomers is utilized to prepare the polymeric products of the present invention.

25- The preparation of the polymeric products of the present invention is intended to promote the esterification reaction between the carboxyl functionality of a saturated monocarboxylic acid and the epoxy functionality derived from an ethylenically unsaturated epoxy functional monomer. is used, thereby forming β-hydroxyl groups in the polymer product. This can be done in several ways, for example: (1) the saturated monocarboxylic acid and the unsaturated epoxy functional monomer are preesterified before polymerization, and the resulting reaction product is (2) Unsaturated epoxy-functional monomers can be polymerized by addition polymerization, for example, by free radical initiated polymerization methods; (2) unsaturated epoxy-functional monomers are typically In particular, one or more hydroxyl-functional vinyl monomers and/or one or more other copolymerizable ethylenically unsaturated monomers (the above components (
and (3) the unsaturated epoxy-functional monomer typically contains one or more hydroxyl-functional vinyl monomers and/or one or more It can be addition polymerized with other copolymerizable ethylenically unsaturated monomers (component (4) above) to form a polymer product having epoxy functionality. This polymer product is subsequently esterified by reaction with a saturated monocarboxylic acid.

Polymerization reactions and nitselization reactions are generally carried out at 80'C-
It is carried out at a temperature of 170°C (preferably 120°C-145°C). Following pre-esterification of this saturated monocarboxylic acid and unsaturated epoxy functional monomer, an early stage of this unsaturated epoxy functional monomer is used to react the resulting adduct with other ethylenically unsaturated monomers. to minimize or avoid polymerization, about 120
It is preferable not to apply temperatures exceeding 10°C. Furthermore, if preesterification is carried out, it is usually carried out in the presence of a catalyst that promotes the epoxy/acid reaction, such as a tertiary amine catalyst, a phosphine catalyst or a tin catalyst. Free radical inhibitors may also be used in pre-esterification to inhibit polymerization.

27- It is preferable to carry out the polymerization reaction and the esterification reaction simultaneously. This is because this operation involves one step rather than two. When carrying out esterification and polymerization simultaneously, the temperature should be high enough to ensure that the polymerization and esterification occur at approximately the same rate.

If desired, esterification catalysts such as tertiary amine catalysts, phosphine catalysts or tin catalysts may be utilized. However, such catalysts are not necessary if the reaction temperature is high enough (eg, above 130° C.). In carrying out the reaction, the reactive components are typically
It is heated in the presence of a free radical initiator and, optionally, a chain transfer agent, in an organic solvent such that the components and the resulting polymer product are compatible. Typically, the saturated monocarboxylic acid is charged to a reaction vessel along with an organic solvent and heated to reflux, optionally under an inert atmosphere. This ethylenically unsaturated epoxy group a
The hydroquine-functional vinyl monomer and/or other covalently capable ethylenically unsaturated monomer and free radical initiator are slowly added to the refluxing reaction mixture. . After the addition is complete, some additional free radical initiator may be added and the reaction mixture maintained at an elevated temperature to complete the reaction.

Examples of organic solvents that can be used for the preparation of polymeric products include: aromatic hydrocarbons (e.g., xylene, toluene, and naphtha); ketones (e.g.,
Methyl ethyl ketone, methyl amyl ketone, methyl-n
-butyl ketone, and methyl isobutyl ketone); esters (e.g. butyl acetate, hexyl acetate, and heptyl acetate); glyfur ethers and glycol esters (e.g. EVA, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dibutylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, and isobutyl iso-29-butyrate). Alcohols such as lower alcohols and simple glycols (e.g., ethanol, propatool, isopropateol, butanol, ethylene glycol, and propylene glycol) can be used as solvents if desired, but typically , are not preferred here, particularly if the polymeric products of the invention are intended to be used in compositions in combination with polyisocyanate or polyanhydride hardeners.

(Left below) 30- Typically, a free radical initiator is used for the polymerization reaction. Examples of free radical initiators include vinyl polymerization initiators that are soluble in the polymerization medium. Examples of free radical initiators include: azo compounds (e.g., α,α°-azobis(imbutyronitrile), azobis-(α,γ-dimethylvaleronitrile), and
, 2°-azobis(methylbutyronitrile)); peroxides (e.g. benzoyl peroxide, tart-peroxide);
butyl, and cumene hydroperoxide); and tert-butyl peracetate, isopropyl percarbonate, butyl isopropyl peroxycarbonate, and similar compounds. Among the examples of free radical initiators described herein, azo compounds are preferred. The amount of initiator used can vary considerably; however, in most cases it will be about 0, based on the weight of polymerizable monomer solids.
．． Preferably, from 1% to about 10% by weight is used.

chain modifying agent
nt) or a chain transfer agent may be added to the polymerization mixture in order to control the molecular weight of the polymerization product. For this purpose, alkyl mercaptans (e.g. dodecyl mercaptan, tertiary
dodecyl mercaptan, octyl mercaptan, and hexyl mercaptan), and other chain transfer agents such as alpha-methylstyrene dimer cyclopentadiene, allyl acetate, allyl carbamate, and mercaptoethanol. In use, these materials are present in amounts up to 5% by weight, based on the weight of the polymerizable ethylenically unsaturated monomer.

Generally, the polymeric products of the present invention can be prepared by gel permeation chromatography (GP) using polystyrene standards.
C) determined by 3.000 to so, oo.

peak molecular weight, preferably 4,000 to 15,00
It has a peak molecular weight of 0. Low molecular weight products are used in high solids coating compositions (i.e., compositions containing at least 50% by weight total solids, typically from about 50% to 75% by weight).
It is particularly useful in compositions containing % by weight total solids, where the solids content is determined by heating at 110° C. for 60 minutes.

32 The hydroxyl number of the polymer products of this invention can vary within a wide range. However, it is generally in the range of 50-250, typically 100-200. In a preferred embodiment, the hydroxyl number is between 145 and 175 based on 100% polymer solids.

The polymer products of this invention are particularly useful for forming curable or thermoset compositions. For this purpose, the polymer products of the invention are formulated with curing agents that are reactive with the active hydrogens in the polymer, especially those derived from hydroxyl groups. Preferred curing agents are organic polyisocyanates or polyanhydrides.

Polyisocyanates that can be used as curing agents include: aliphatic or cycloaliphatic polyisocyanates (eg, hexamethylene diisonanate and dicyclohexylmethane diisocyanate); aromatic polyisocyanates (eg, 2. 4-
and 2.6-toluene diisocyanate and mixtures thereof, and 33 and diphenylmethane-4,4′-diisocyanate);
arylalkyl polyisocyanates (e.g. ortho-meta- and para-xylylene diisocyanates);
Isophorone diisocyanate: A polyurethane polyisocyanate obtained by reacting a polyisocyanate as described above with a polyhydroxy compound (eg, ethylene glycol and trimethylolpropane). Polyisocyanates containing incyanurate groups, allophanate groups or biuret groups can also be used.

When a polyisocyanate is used as a curing agent in a composition containing the polymeric product of the invention, to promote curing between the hydroxyl groups of the polymeric product and the incyanato groups of the polyisocyanate. An effective amount of catalyst may be mixed.

Examples of such catalysts include: tertiary amines (e.g. triethylamine) or 1,4-diazobicyclo-(2:2:2) octane, and organotin compounds (e.g. octanoic acid). stannous (stan34-nous octoate and dibutyltin dilaurate).

Examples of polyanhydrides that can be used as curing agents for the polymeric products of this invention include carboxylic acid anhydrides that are monomeric, oligomeric, or polymeric. Specific examples of carboxylic acid anhydrides include: isoprene disuccinic anhydride, and pyromellitic anhydride. Other specific examples of polyanhydrides include, for example, the reaction of ethylenically unsaturated carboxylic acid anhydrides (e.g. maleic anhydride, citraconic anhydride and itaconic anhydride) with, e.g. vinyl and/or acrylic monomers. Included are polymers containing anhydride groups derived from. For example, the carboxylic anhydride component may be a mixture of a monomer containing an ethylenically unsaturated carboxylic anhydride and at least one vinyl comonomer (e.g., styrene, alpha-methylstyrene, vinyltoluene, vinyl acetate, and vinyl chloride). can be derived from. By acrylic monomers is meant compounds such as acrylic and methacrylic acids and their ester derivatives, acrylamide and methano-35-lylamide, and unsaturated nitrites (eg, acrylonitrile and methacrylonitrile). Examples of acrylic monomers include: hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, Isopropyl (meth)acrylate,
Butyl (meth)acrylate, (meth)acrylic acid t
-butyl, 2-ethylhexyl (meth)acrylate,
n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, (meth)acrylic acid 3.3.5
-) Limethylcyclohexyl, (meth)decyl acrylate, (meth)isodecyl acrylate, (meth)
These are lauryl acrylate, stearyl (meth)acrylate, phenyl (meth)acrylate, and imbornyl (meth)acrylate.

Other examples of carboxylic acid anhydrides include anhydride adducts of diene polymers, such as maleated polybutadiene or maleated butadiene copolymers (e.g., butadiene/styrene copolymers). ); and anhydride adducts of unsaturated fatty acid esters, such as maleated styrene/allylic alcohol copolymers esterified with unsaturated fatty acids.

When a polyanhydride is used as a curing agent in a composition containing the polymeric product of the invention, it promotes curing between the hydroxyl groups of the polymeric product and the anhydride groups of the polyanhydride. An effective amount of catalyst may be mixed to effect the reaction. Examples of such catalysts include: amines, typically tertiary amines (e.g. dimethylcocoamine, triethylamine, triethanolamine, and phenolic compounds containing dialkylamino groups) It is. When an amino-functional ethylenically unsaturated monomer is used in preparing the polymeric product of the present invention, the amino-7 group incorporated into the polymeric product is It can act as an "internal" curing accelerating catalyst in a product. Examples of such amino-functional ethylenically unsaturated monomers 37 include dimethylaminoethyl niaacrylate, diethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, tert-methacrylate. butylaminoethyl, and dimethylaminopropyl methacrylamide.

Other curing agents that are reactive with active hydrogen in the polymeric products of this invention include aminoblast resins, which are aldehyde condensation products of amines or amides with aldehydes. Examples of suitable amines or amides include melamine, benzoguanamine, urea and similar compounds. Generally, the aldehyde used is formaldehyde. However, the product may also be made from other aldehydes, such as acetaldehyde and furfural. Depending on the particular aldehyde used, the condensation product is
Contains a methylol group or similar alkylol group.

If desired, these methylol groups can be etherified by reaction with an alcohol. A variety of alcohols may be used, generally including any alcohol. However, the preferred alcohol is 1
Examples are methanol, ethanol, impropatol, and n-butanol. Amino Blast is made from American cyanamide (Ame
It is commercially available under the trademark CYMEL from Cyanamid and Monsanto Chemical.
It is commercially available under the trade name RESIMINE from the Company to Chemical Co., Ltd.

Such curable (crosslinkable) or thermosetting compositions are particularly useful as coating compositions.

For painting applications, the composition may be formulated as a transparent coating or optionally contain pigments.

The pigment is any conventional type of pigment. For example, iron oxide, lead oxide, strontium chromate, carbon black, charcoal dust, titanium dioxide, talc, barium sulfate, and colored pigments (e.g., cadmium yellow, cadmium red, chrome yellow, phthalocyanine blue, toluidine red), arsenic 9- pigments such as aluminum foil, mica encapsulated with metal oxides. The pigment content of a coating composition in use is expressed as a weight ratio of pigment to resin and is usually
It is within the range of about 005 to 3.0:1. The pigmented coating compositions of the present invention can be applied, for example, to 120°F (48.9°F).
It has been found that such compositions exhibit excellent thermal stability, as evidenced by the substantial absence of color drift of such compositions upon heat aging for 7 days at <0.05°C.

Additionally, other optional ingredients such as auxiliary hydroxy-containing polymers, fillers, plasticizers, catalysts, reactive diluents, antioxidants, UV absorbers, flow control agents, and other formulation additives may be included. Can be used if desired.

The coating compositions of the invention contain the polymer products of the invention as binders. The amounts of polymer product and curing agent in the compositions of the present invention can be varied.

Typically, however, the polymeric product and curing agent, based on their combined solids weight,
Each is present in an amount of 40-75 percent (preferably 40-70 percent) and 60-25 percent (preferably 40-30 percent).

In a typical embodiment of the pigmented coating composition of the present invention, the composition contains, based on the total weight of the coating composition,
20% to 80% by weight (preferably 40% to 6% by weight)
0% by weight) of the polymer product solids, up to 50% by weight pigment, and from 20% to 80% (preferably 4% by weight)
0% to 60% by weight) of solvent and/or diluent.

The coating compositions of the present invention can be applied to a variety of substrates (e.g., wood, metal, glass, fabric, plastic) by a variety of application methods (e.g., air spray, airless spray, dip coating, brushing, and flow coating). , foam, etc.). Typically, this coating composition is applied by spraying. This coating composition is particularly desirable as a top coat composition for automobiles and trucks, either as a first finish or as a refinish coat.

The hydroquine-functional, thermosetting (i.e., crosslinkable) polymeric products of the present invention, when cured, produce durable, high-quality automotive finishes with very high gloss and dots. and a high degree of buffing is required to obtain such excellent appearance properties.
does not require.

The coating composition of the present invention is a coating composition that is becoming popular in the automobile industry.
A coating system known as ``Color Plus Clear'' has been found to be useful.

In this system, the substrate is coated with one or more coats of a pigmented basecoat composition to form a basecoat, followed by one or more coats of a substantially clear topcoat composition. A topcoat is formed by applying a layer of paint. The coating compositions of the present invention may be utilized as either or both pigmented basecoat compositions and clear topcoat compositions. The coating composition of the present invention may, for example, in particular:
It has been found useful as a clear topcoat composition.

This topcoat composition may be applied to the basecoat either before or after the basecoat has dried or cured.

-42= The invention therefore also provides a coating method comprising the following steps (A> and <8): (A) a film-forming resin, which comprises a polymer product of the invention; a pigmented basecoat composition containing (same or different);
applying one or more coats to a substrate to form a basecoat; then (B) (a) a polymeric product of the invention; (b) reactive with the hydroxyl functionality of the polymeric product; a curing agent (as described above), and (c) optionally,
This is a step of applying a topcoat composition containing a curing accelerating catalyst to the undercoat one or more times. In a preferred embodiment of the process of the invention, the polymer product is
(1) saturated monocarboxylic acid 10% by weight to 40ff%,
(2) 5% to 25% polymerizable ethylenically unsaturated epoxy-functional monomer, (3) 10% to 40% copolymerizable axyl-functional vinyl monomer, and ( 4) 20% to 5% by weight of a copolymerizable ethylenically unsaturated monomer different from components (2) and (3)
It is formed from components containing 0 MM%. The curing agent is an organic polyisocyanate (an example is 4
3- Contains (as described above). The methods of the present invention also include "color plus clear" methods in which the polymeric products of the present invention are utilized in a basecoat composition and a film-forming resin other than the polymeric product of the present invention is used. is utilized in transparent topcoat compositions.

Therefore, at least one of the basecoat composition and topcoat composition may be used as the only film-forming resin or, optionally, with other film-forming thermoplastic resins and/or
or containing the polymer product of the present invention in combination with a thermosetting resin. Examples of such other film-forming thermoplastics and/or thermosetting resins include commonly known cellulose compounds, acrylics, aminoblasts, urethanes, polyesters, polyethers, epoxides or Mixtures thereof are included.

Additionally, if only one of the basecoat composition and the topcoat composition contains the copolymer product of the present invention, the other composition may include the commonly known cellulosic compounds, acrylics, etc. mentioned above. , aminoplasts, urethanes, polyesters, epoxides or mixtures thereof. These film-forming resins may be used, if desired, in combination with various ingredients commonly known for use in coating compositions containing these common lath film-forming resins. Examples of these various ingredients include: fillers; plasticizers; antioxidants; fungicides and fungicides; surfactants; and various flow control agents, including, for example, These include additives for anti-sag and/or pigment orientation based on thixotropic agents and polymeric microparticles (sometimes designated as microgels).

These polymer fine particles are described, for example, in U.S. Patent No. 4,02
No. 5.474; No. 4.055.6Q'7; No. 4,07
No. 5.141; No. 4.115.472; No. 4, 147
．． No. 688: No. 4.180.489; No. 4.242.
No. 384; No. 4, 268.547; No. 4.220.6
No. 79; and No. 4.290.932, the contents of which are hereby incorporated by reference.

Pigments suitable for 5-3 colored basecoat compositions include a wide range of pigments commonly known for use in coating compositions.

Pigments include both metal foil pigments and a variety of white and colored pigments, examples of which are described above.

The following examples illustrate the invention and are not to be construed as limitations on its scope. It is to be understood that all percentages and amounts are by weight unless otherwise indicated. rpbwJ as used herein means parts by weight.

EXAMPLE X Huangyuan Gong This example illustrates the preparation of a resinous product (acrylic polyol) in accordance with the present invention.

In a reaction vessel equipped with a stirrer, a thermometer, a condenser, and an addition funnel, add 1126.3 g of quintessence and 505,0 g of dihysostearic acid (which was prepared by Emily Industries).
EMER5O from ery Industries>
L 875) and heated to reflux (approximately 140'C). Two feedstocks, identified herein as "Feedstock A" and "Feedstock B", are gradually and simultaneously added to the vessel over a period of 2 hours. During this time, the contents of the container are maintained at reflux.

Feedstock A consists of a mixture of 729.8 g of styrene, 526.8 g of hydroxypropyl acrylate, 241.5 g of methyl methacrylate and 252.0 g of glycidyl methacrylate. Feedstock B is 2.
It consists of a mixture of 87.5 g of 2°-azobis(methylbutyronitrile) and 351°5 g of xylene. After the addition of the two feedstocks A and B is complete, the contents of the vessel are refluxed and the acid number is monitored until it falls below 4.0 (after about 6 hours). The product obtained is cooled and diluted with 279.8 g of xylene.

The product obtained has a total solids content of 1t56.3% by weight, determined after standing for 1 hour at 110°C. In this product, the residual methyl methacrylate and styrene contents are 0.15% and 0.31% by weight, respectively. This product contains 3.10 mg KOH/g
Acid number of T, Gardner-Holdt bubble tube viscosity of 7 77.7 mg KOH/g Hydroxyl number of 17.
It has an epoxy equivalent weight of 234 and an APHA color number of 30-40. and the peak molecular weight of 9827, 11.434
and a number average molecular weight of 5123 (determined by gel permeation chromatography using polystyrene standards).

Section (a) of this example illustrates the preparation of a two-pack topcoat composition in accordance with the present invention. (b) of this example
Section (a) illustrates the application, curing and resulting properties of the topcoat composition of section (a).

(a) Mix together the ingredients shown in Table 1 below.

Table 1 Reaction product of Example 1 of 127.6 67.4 68.7 Curing agent 379.0 Colored package 1 Diluent 2 Polyisocyanate 8 1) Colored package is 612 .5 pbw of butyl acetate, 102.5 pbv of acetylbutyl cellulose (Eastman Chemical)
(available as CAB 551.01 from Al)
, 452.5 pbw xylene, 100.0 pbw butanol, 160.0 pbw aluminum pigment paste (Silver Line Manufacturing (Si
3166 AR5parkle 5ilver), 65.0 pbw butyl cellosolve acetate, 67.5 pbv DOWANOLPM acetate, 57.5 pbw tin catalyst solution (4,55 pb
y of dibutyltin dilaurate, 228.6 pbw of DOWANOL PM Acetate and 224.05
pbv of xylene), 15.0 pbw of flow control agent (BYK Mallinckrodt Chem, Produ.
(available as BYK 300 from CIBA-GEIGY), 30.0 pbw UV absorber (TIN0VI from CIBA-GEIGY)
N328), 15.0 pbv of hindered amine stabilizer (TIN from Ciba Geigy)
UVIN 292), and 7.5g
AROMATIC-100 (a mixture of aromatic hydrocarbons commercially available from Exxon Chemical Company, USA).

2) 2 o, o parts by volume of lactol spirits, 15.0
parts by volume of toluene, 10,0 parts by volume of butyl acetate, 20 parts by volume
．． A mixture of 0 parts by volume of DOWANOL PM acetate and 35.0 parts by volume of methyl ethyl ketone.

3) The curing agent was aliphatic polyisocyanate 358.0 pbw (Mobil Chemical Co., Ltd.) in 302.48 pbw butyl acetate and 80.16 pbw ethyl acetate.
DESMODURN from Bay Chemical
-3200).

(b) Spray the top coating composition of item (a) above the scoop onto the following 24-gauge cold-rolled steel plate at room temperature and normal pressure. The steel plate is treated, primed, sanded and flushed normally for 3-5 minutes between coats.
3 double coatings (i.e. BON
Processed with DERITE 40, from PPG Industries, Inc., PPG FINISHES -200/-2
Primed with a two-pack acrylic urethane undercoat surfacer available as
0 Polished with rad paper and polished by PPG Industries, PP
(sealed with a two-part epoxy primer available as DP-407401 from G FINISHES)
.

The composite film obtained from the top coating composition in section (a) is:
It is cured and the resulting properties are measured. The results are shown in Table 2 below. The following terms and abbreviations used in Table 2 have the meanings indicated below.

"Dust-free" means the time (in minutes) required for a cotton ball placed on a painted board for 10 seconds to separate from the board when the board is turned upside down.

"Tack time" means the time (in minutes) until the paint no longer feels viscous to the touch.

r DFTJ means dry film thickness (mils).

"200 gloss" means that after applying the topcoat composition to the board,
Means "20 degree gloss" measured conventionally after 24 hours and after 8 days, respectively.

rDOIJ means that after applying the topcoat composition to the board,
Means "image sharpness" measured conventionally after 51 hours and after 8 days, respectively.

"Suode" means that after applying the topcoat composition to the board,
Means the "sword hardness" measured in a conventional manner after 4 hours and after 8 days, respectively.

"Pencil" means "pencil hardness" conventionally measured 24 hours and 8 days after application of the topcoat composition to the board, respectively.

"Gasoline" refers to the composite film's resistance to degradation by soaking it in gasoline for 3 minutes. Regarding gasoline immersion, a rating of 5 means excellent, a rating of 4 is good, a rating of 3 is fair, a rating of 2 is poor, and a rating of 1 is extremely poor.

"Tack" refers to the cross-hatch adhesion of the composite film to the substrate, determined according to ASTM Test Method D Method 59, after 24 hours and 8 days, respectively, after painting. Evaluation values for this test range from 0 to 5. A rating of 5 for this test means that there is no lack of adhesion of the composite coating (i.e., "pick orf") using either method.
J is missing).

"Wettability" means resistance to moisture as determined using a humidity chamber operating at 37.8°C and 100 percent relative humidity. The values in the table are the 20 degree gloss readings of the composite coating before it was placed in the humid chamber (ie, 0 hours) and after 96 hours in the humid chamber.

"Adhesive-H" means that this composite coating is placed in the above-mentioned humidity chamber.
Means the cross-/% latch adhesion of the composite film to the substrate as determined according to ASTM Test Method D Method 59 after 1 hour and 24 hours, respectively.

"Toluene" refers to the solvent resistance of a coating when two drops of toluene are applied to the coating and allowed to evaporate.

An evaluation value of 5 means that there is no visible effect (deterioration) on the coating in this test.

(Blank below) 53- Table 2 Table 2 (Continued) Table 2 (Continued) Table 2 (Continued) (a) Section 80/79 15 *Not measured -54= (Summary of the invention) Saturated monocarboxylic acid, polymerization reacting a possible ethylenically unsaturated epoxy functional monomer, optionally a copolymerizable hydroxyl functional vinyl monomer and optionally at least one other copolymerizable ethylenically unsaturated monomer. disclose a resinous composition containing a polymeric product prepared by . The preparation of the polymer product involves, in part, the reaction of carboxyl functionality derived from the saturated monocarboxylic acid with epoxy functionality derived from an ethylenically unsaturated epoxy functional monomer.

Furthermore, coating compositions containing this polymer product as a binder are disclosed.

Additionally, a "color plus clear" coating process using this polymer product is disclosed.

that's all

Claims (1)

Claims: 1. (A) 20% by weight of a polymer product formed from the reaction of components comprising (1), (2), (3) and (4):
and (B) 80% to 0% by weight of an inert organic solvent; (1) a saturated monocarboxylic acid; (2) a polymerizable ethylenically unsaturated epoxy functionality. monomer, (3) optionally a copolymerizable hydroxyl functional vinyl monomer, and (4) optionally a copolymerizable ethylenically unsaturated monomer different from said components (2) and (3). ;here,
The epoxy functionality from the ethylenically unsaturated epoxy functional monomer has reacted with the carboxyl functionality from the saturated monocarboxylic acid, and the ethylenic unsaturation from the epoxy functional monomer and the Any ingredient (
The ethylenic unsaturation derived from 3) and (4) undergoes addition polymerization in the presence of a polymerization initiator. 2. The polymer product has the following (1), (2), (3)
) and (4): (1) 1.0% to 70% by weight of the saturated monocarboxylic acid; (2) the polymerizable monocarboxylic acid; 1.0% to 50% by weight of an ethylenically unsaturated epoxy functional monomer, (3) 0% to 40% by weight of said copolymerizable hydroxyl functional vinyl monomer, and (4) said component (2) and 0% to 60% by weight of the copolymerizable ethylenically unsaturated monomer different from (3)
. 3. The resinous composition of claim 2, wherein said polymeric product is formed from said components containing from 10% to 40% by weight of said hydroxyl-functional vinyl monomer. 4. The polymer product contains the components (2) and (3)
4. The resinous composition of claim 3, wherein said component comprises 20% to 50% by weight of said copolymerizable ethylenically unsaturated monomer different from . 5. The resinous composition according to claim 2, wherein the polymerization initiator includes a free radical polymerization initiator. 6. The polymer product has the following (1), (2), (3)
) and (4): (1) 10% to 40% by weight of the saturated monocarboxylic acid;
, (2) 5.0% to 25% by weight of said polymerizable ethylenically unsaturated epoxy functional monomer, (3) 10% to 40% by weight of said copolymerizable hydroxyl functional vinyl monomer, and (4) ) 20% to 50% by weight of said copolymerizable ethylenically unsaturated monomer different from said components (2) and (3). 7. A method for preparing a polymeric product suitable for use in a thermosetting composition, comprising: (1)
, (2), (3) and (4): (1) a saturated monocarboxylic acid; (2) a polymerizable ethylenically unsaturated epoxy functional monomer; (3) optionally a copolymerizable hydroxyl-functional vinyl monomer, and (4) optionally a copolymerizable ethylenically unsaturated monomer different from said components (2) and (3);
The epoxy functionality from the ethylenically unsaturated epoxy functional monomer reacts with the carboxyl functionality from the saturated monocarboxylic acid and reacts with the ethylenic unsaturation from the ethylenically unsaturated epoxy functional monomer. , the ethylenically unsaturated components derived from the optional components (3) and (4) undergo addition polymerization in the presence of a polymerization initiator. 8. The saturated monocarboxylic acid and the polymerizable ethylenically unsaturated epoxy functional monomer are first preesterified to form a first reaction product, and the first reaction product is Then, in the presence of the polymerization initiator,
polymerizing together with the optional components (3) and (4);
The method according to claim 7. 9. The polymerizable ethylenically unsaturated epoxy-functional monomer is first polymerized with optional components (3) and (4) to form an epoxy-functional polymerized product, and then the epoxy-functional 8. The method according to claim 7, wherein the saturated monocarboxylic acid is esterified with the saturated monocarboxylic acid. 10. The ethylenically unsaturated epoxy functional monomer comprises the saturated monocarboxylic acid and the optional component (3)
The method according to claim 7, wherein the polymerization is carried out in the presence of and (4). 11. A coating composition containing as a binder a polymer product formed from the reaction of components comprising (1), (2), (3) and (4): (1) a saturated monocarboxylic acid; (2) a polymerizable ethylenically unsaturated epoxy functional monomer; (3) optionally a copolymerizable hydroxyl functional vinyl monomer; and (4) optionally said components (2) and (3). copolymerizable ethylenically unsaturated monomer different from );
In the polymer product, the epoxy functionality derived from the ethylenically unsaturated epoxy functional monomer has reacted with the carboxyl functionality derived from the saturated monocarboxylic acid, and the ethylenically unsaturated epoxy functionality Ethylenic unsaturation derived from the monomer and the optional components (3) and (4)
Ethylenic unsaturation derived from is addition polymerized in the presence of a polymerization initiator. 12. The polymer product has the following (1), (2), (
12. The coating composition according to claim 11, formed from the components containing 3) and (4): (1) 1.0% to 70% by weight of the saturated monocarboxylic acid; (2) the polymerizable monocarboxylic acid; 1.0% to 50% by weight of an ethylenically unsaturated epoxy functional monomer, (3) 0% to 40% by weight of said copolymerizable hydroxyl functional vinyl monomer, and (4) said components (2) and ( 3) The copolymerizable ethylenically unsaturated monomer different from 0% to 60% by weight
. 13. The coating composition according to claim 12, further comprising a pigment. 14. The coating composition of claim 12, wherein the polymer product is formed from components containing from 10% to 40% by weight of the copolymerizable hydroxyl-functional vinyl monomer. 15. The polymer product comprises components (2) and (3).
) 20% by weight of said ethylenically unsaturated monomer different from
Claim 14 formed from components containing ~50% by weight.
The coating composition described in . 16. The coating composition according to claim 12, wherein the polymerization initiator includes a free radical polymerization initiator. 17. The polymer product has the following (1), (2), (
The coating composition according to claim 12, formed from components containing 3) and (4): (1) 10% to 40% by weight of the saturated monocarboxylic acid;
, (2) 5.0% to 25% by weight of said polymerizable ethylenically unsaturated epoxy functional monomer, (3) 10% to 40% by weight of said copolymerizable hydroxyl functional vinyl monomer, and (4) ) 20% to 50% by weight of said copolymerizable ethylenically unsaturated monomer different from said components (2) and (3). 18. The coating composition of claim 17, comprising a curing agent reactive with the hydroxyl functionality of the polymer product. 19. The coating composition according to claim 18, wherein the curing agent comprises an organic polyisocyanate. 20, the polymer product and the curing agent each have a content of 40 to 40, based on their combined solid weight;
19. The coating composition of claim 18, comprising 75 percent and 25 to 60 percent by weight. 21. 20% by weight based on the total weight of the coating composition
21. The coating composition of claim 20, containing ~80% solids of the polymer product, up to 50% pigment, and 20% to 80% solvent. 22. (A) applying a colored undercoat composition containing a film-forming resin to a substrate in one or more coats to form an undercoat; and (B) following (a) and (b). and (c) coating the basecoat with one or more coats of a topcoat composition containing: (a) (1) saturated monocarboxylic acid 1.0 (2) 1.0% to 50% by weight of polymerizable ethylenically unsaturated epoxy functional monomer; (3) 0% to 40% by weight of copolymerizable hydroxyl functional vinyl monomer.
% by weight, and (4) from 0% by weight of a copolymerizable ethylenically unsaturated monomer different from said components (2) and (3).
A polymer product formed from components containing 60% by weight of epoxy functional groups derived from the ethylenically unsaturated epoxy functional monomer in the polymer product containing 60% by weight of the saturated monocarboxylic acid. (b) a curing agent reactive with the hydroxyl functionality of the polymeric product; and (c) optionally an effective amount of a curing accelerating catalyst. 23. The polymer product has the following (1), (2), (
23. The method of claim 22, formed from components comprising: (1) the saturated monocarboxylic acid 1.
0% to 70% by weight, (2) 1.0% to 50% by weight of said polymerizable ethylenically unsaturated epoxy functional monomer, (3) 0% to 50% by weight of said copolymerizable hydroxyl functional vinyl monomer. 40% by weight, and (4) 0% to 60% by weight of said copolymerizable ethylenically unsaturated monomer different from said components (2) and (3). 24. The polymer product has the following (1), (2), (
23. The method of claim 22, wherein the curing agent comprises: (1) 10% to 40% by weight of the saturated monocarboxylic acid;
, (2) 5.0% to 25% by weight of said polymerizable ethylenically unsaturated epoxy functional monomer, (3) 10% to 40% by weight of said copolymerizable hydroxyl functional vinyl monomer, and ( 4) 20% to 50% by weight of said copolymerizable ethylenically unsaturated monomer different from said components (2) and (3). 25, the polymer product and the curing agent each have a content of 4% by weight, based on their combined solids weight.
25. The method of claim 24, containing from 0 to 75 percent and from 25 to 60 percent by weight.